Synthesis of new chiral pincer-complex catalysts for asymmetric allylation of sulfonimines

Four new chiral pincer-complexes were prepared based on coupling of BINOL and TADDOL moieties with iodoresorcinol followed by oxidative addition of palladium(0). The X-ray analysis of complex 5a revealed that the BINOL rings form a well-defined chiral pocket around the palladium atom. This chiral environment can be further modified by γ-substitution of the BINOL rings. Preliminary studies for electrophilic allylation of sulfonimine 2 with allylstannane revealed that the presented chiral complexes are promising asymmetric catalysts for preparation of chiral homoallyl amines. The best result was achieved employing catalytic amounts of γ-Me BINOL complex 6 affording homoallyl amine 4 with 59% ee and 74% isolated yield.

Graphical abstractBINOL and TADDOL based chiral palladium pincer-complexes were synthesized for asymmetric allylation of sulfonimines. The methyl substituted complex (R = Me) catalyzes the reaction of tributyl allylstannane and benzene sulfonimine affording homoallylamine product with 59% ee and 74% isolated yield.Figure optionsDownload full-size imageDownload as PowerPoint slide